CN114778652B - Preparation method and application of laser direct writing patterned nano gold@reduced graphene oxide paper-based electrochemical sensor - Google Patents
Preparation method and application of laser direct writing patterned nano gold@reduced graphene oxide paper-based electrochemical sensor Download PDFInfo
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Abstract
The invention belongs to the technical field of patterning paper-based flexible electronic preparation, and particularly discloses a preparation method and application of a laser direct writing patterning nano gold@reduced graphene oxide paper-based electrochemical sensor. The method comprises the following steps: mixing graphene oxide with cellulose pulp, and adding a bonding agent to obtain graphene oxide paper; and then immersing the graphene oxide paper in chloroauric acid solution, and performing laser patterning reduction. Gold nanoparticles are inoculated on the surface of graphene while reducing graphene oxide; and then the patterned reduced paper electrode is put into chloroauric acid, so that the nano gold grows on the surface of the paper electrode to obtain an electrochemical sensor, and the electrochemical sensor can be used for electrochemical sensing detection of hydrogen peroxide. According to the invention, the laser is utilized to reduce graphene oxide, and meanwhile, the gold nanoparticles are inoculated on the surface of the graphene, so that the patterned growth of the gold nanoparticles on the surface of the electrode is promoted. According to the invention, a reducing agent is not required to be added, the process for modifying the nano gold is simplified, and the nano gold modified on the surface of the obtained sensor is more uniform.
Description
Technical Field
The invention belongs to the technical field of patterning paper-based flexible electronic preparation, and particularly relates to a preparation method and application of a laser direct writing patterning nano gold@reduced graphene oxide paper-based electrochemical sensor.
Background
The paper-based electrochemical sensor is a sensing device which takes cellulose paper as a substrate to load conductive materials as electrodes for accurately detecting chemical substances. Compared with the traditional electrochemical sensor, the paper-based electrochemical sensor has the advantages of low cost, convenient carrying, disposability and the like, so that the paper-based electrochemical sensor can be widely applied to the fields of health detection, food safety, environmental protection and the like. At present, a screen printing method is mainly adopted for preparing the paper-based sensor. However, due to the diversity of the paper substrate and the conductive ink, the sensors prepared in different batches have obvious differences, thereby affecting the commercial application of the paper-based electrochemical sensor.
Graphene oxide is a graphene derivative having a large number of oxygen-containing functional groups. The preparation of graphene oxide by a chemical oxidation method has become one of the main production processes for the current preparation of graphene. The graphene oxide has good water dispersibility, so that the further processing and utilization of the graphene oxide are facilitated. However, due to the presence of the oxygen-containing functional group, the interlayer gap of the graphene oxide sheet is larger, so that the graphene oxide sheet does not have the property of electric conduction, and the application of the graphene oxide product is limited. In order to solve the problem, the current technology mainly adopts a chemical method to reduce the graphene oxide, and removes oxygen-containing functional groups on the surface of the graphene oxide to enable the graphene oxide to have high conductivity. However, the reduction method is costly in terms of production process and cannot be used for patterning. The preparation of patterned graphene electrodes based on laser thermal reduction has gradually become the current hotspot direction. However, the laser direct writing reduction method of graphene oxide paper compounded with cellulose still has a plurality of problems in an air environment. This is because cellulose burns at high temperatures due to the presence of oxygen, resulting in failure of the patterned electrode preparation.
Nanogold (Au NPs) is a common electrochemical sensor modification material. The nano gold is modified on the surface of the electrochemical sensor, so that the sensitivity and electrochemical activity of the sensor can be improved. The traditional method mainly adopts an electrodeposition method and a mixed ink printing method to modify Au NPs on the surface of the paper-based electrochemical sensor. However, the complicated manufacturing process makes the manufactured paper-based sensor less uniform, and thus makes the manufactured paper-based electrochemical sensor unusable for commercial applications. Therefore, there are still many problems how to prepare high-precision patterned Au nps@reduced graphene oxide paper-based electrochemical sensors.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a laser direct writing patterned nano gold@reduced graphene oxide paper-based electrochemical sensor.
The invention further aims to provide the nanogold@reduced graphene oxide paper-based electrochemical sensor prepared by the method.
The invention further aims to provide application of the nanogold@reduced graphene oxide paper-based electrochemical sensor in hydrogen peroxide detection.
The aim of the invention is achieved by the following scheme:
a preparation method of a nanogold@reduced graphene oxide paper-based electrochemical sensor comprises the following steps:
(1) Preparation of graphene oxide paper:
dispersing cellulose pulp in water, adding graphene oxide, and continuously stirring to uniformly mix the graphene oxide and cellulose; adding a bonding agent, and continuously stirring until the water becomes clear to obtain slurry; pouring the slurry into a paper sheet forming machine for papermaking, and drying to obtain graphene oxide paper;
(2) Adsorbing gold ions:
immersing the graphene oxide paper in the step (1) in chloroauric acid solution to enable the graphene oxide paper to fully absorb the chloroauric acid solution;
(3) Patterning and reducing chloroauric acid and graphene oxide by a laser direct writing method;
spreading the graphene oxide paper adsorbed with the chloroauric acid solution in the step (2) on the surface of glass, and placing the graphene oxide paper into a laser direct writing machine for patterning reduction to obtain a patterned reduced graphene oxide electrode containing nano gold particles;
(4) Growth of nano gold:
and (3) placing the patterned reduced graphene oxide electrode containing the nano gold particles in the step (3) into chloroauric acid solution, and finally obtaining the Au NPs@reduced graphene oxide paper-based electrochemical sensor after the surface of the electrode is changed from gray to golden yellow and dried.
Preferably, the binding agent in the step (1) is at least one of cationic polyacrylamide, chitosan, dopamine and polyethyleneimine.
Preferably, the concentration of the binding agent in the slurry in the step (1) is 0wt% to 1wt% and is not 0.
Preferably, the cellulose pulp concentration in the slurry of step (1) is 0.05wt% to 0.3wt%.
Preferably, the concentration of graphene in the slurry in the step (1) is 0.5g/L-15g/L.
Preferably, the chloroauric acid solution in the step (2) has a concentration of 0g/L to 5g/L and is not 0.
Preferably, the soaking time in the step (2) is 1min-60min.
Preferably, the output power of the laser direct-write machine in the step (3) is 100mW-800mW, and the writing speed is 5mm/s-200mm/s. The laser direct writing reduction is performed in an air environment, and the graphene oxide paper needs to be completely wetted.
Preferably, the concentration of the chloroauric acid solution in the step (4) is 0.1g/L-5g/L.
Preferably, the time for changing the surface of the electrode from gray to golden in the step (4) is 5-60 min.
The nano gold@reduced graphene oxide paper-based electrochemical sensor is prepared by the method, wherein the content of graphene oxide is 10% -70%, and the other is cellulose; more preferably, the graphene oxide content is 30% and the chloroauric acid concentration is 0.5g/L.
The invention further provides application of the nano gold@reduced graphene oxide paper-based electrochemical sensor in electrochemical sensing of hydrogen peroxide.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the graphene oxide is reduced by a laser thermal reduction method and simultaneously inoculated with the gold nanoparticles, and the temperature during laser reduction is reduced by using the solution adsorbed in the paper base, so that the laser patterning reduction of the graphene oxide paper in an air environment becomes possible, and the process steps for preparing the electrochemical sensor are reduced.
(2) During the modification of the nano-gold, no reducing agent is added. By means of patterning the huge potential difference between the reduced graphene and chloroauric acid, the unstable chloroauric acid is reduced to nano-gold and grown near the gold seeds of the reduced graphene oxide region. The method avoids the use of reducing agent, controls the growth area of chloroauric acid, and reduces the use amount of chloroauric acid.
(3) The Au NPs@reduced graphene oxide paper-based electrochemical sensor prepared by the method has good conductivity and uniformity, and electrochemical sensors in different batches show excellent stability in electrochemical detection experiments.
Drawings
Fig. 1 is a physical diagram of an Au nps@reduced graphene oxide paper-based electrochemical sensor prepared in example 1.
Fig. 2 is a scanning electron microscope image of the surface of the Au nps@reduced graphene oxide paper-based electrochemical sensor prepared in example 1.
FIG. 3 is a Raman spectrum of the Au NPs@reduced graphene oxide paper-based electrochemical sensor prepared in example 1.
Fig. 4 is a physical diagram of the Au nps@reduced graphene oxide paper-based electrochemical sensor prepared in comparative example 1.
Fig. 5 is a physical diagram of an Au nps@reduced graphene oxide paper-based electrochemical sensor prepared in comparative example 2.
FIG. 6 is an electrochemical sensing diagram of Au NPs@reduced graphene oxide paper-based electrochemical sensors prepared in example 1 (a) and comparative example 2 (b).
FIG. 7 is an electrochemical sensing detection diagram of the Au NPs@reduced graphene oxide paper-based electrochemical sensor prepared in example 1 on hydrogen peroxide; wherein (a) is a time current curve of hydrogen peroxide detection, and (b) is an anti-interference test of hydrogen peroxide detection.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
Preparation of Au NPs@reduced graphene oxide paper-based electrochemical sensor:
(1) Preparation of graphene oxide paper:
1.4g of cellulose pulp was dispersed in 1L of water and stirred rapidly at room temperature; adding 60mL of graphene oxide solution with the concentration of 10g/L, and continuously stirring to uniformly mix graphene oxide and cellulose; adding 2ml of cationic polyacrylamide with the concentration of 1wt% as a binding agent, and continuously stirring until water becomes clear, so that graphene oxide is completely compounded on the surface of cellulose; pouring the mixed slurry into a paper sheet forming machine, and forming and drying to obtain graphene oxide paper;
(2) Adsorbing gold ions:
immersing the graphene oxide paper in the step (1) in 0.1g/L chloroauric acid solution for 1min to enable the graphene oxide paper to fully absorb the chloroauric acid solution;
(3) Patterning and reducing chloroauric acid and graphene oxide by a laser direct writing method;
taking out the graphene oxide paper adsorbed with the chloroauric acid solution in the step (2), spreading the graphene oxide paper on the surface of glass after no liquid drops drop from the graphene oxide paper, and placing the graphene oxide paper into a laser direct writing machine for pattern reduction, wherein the output power of laser direct writing is 500mW, and the speed is 20mm/s, so as to obtain a patterned reduced graphene oxide electrode containing a small amount of gold nanoparticles;
(4) Growth of nano gold:
and (3) placing the patterned electrode in the step (3) into 1g/L chloroauric acid solution, changing the surface of the electrode from gray to golden yellow after 30min, taking out the electrode, repeatedly flushing the electrode with clear water, and then placing the electrode into an oven for drying to finally obtain the Au NPs@reduced graphene oxide paper-based electrochemical sensor.
(5) Electrochemical detection:
and connecting the working electrode of the prepared Au NPs@reduced graphene oxide paper-based electrochemical sensor with the working electrode of an electrochemical workstation, wherein a counter electrode and a reference electrode are respectively a platinum electrode and a silver/silver chloride electrode. The connected three electrodes were placed in a 1M sodium chloride solution and cycled at a rate of 100mV/s for 30 cycles over a voltage range of-0.2-0.7V. After the voltammograms are matched, 5mM potassium ferricyanide is added and voltammograms are tested using different scan rates over the same voltage range.
From fig. 1 and fig. 2, it can be known that the pattern precision of the prepared Au nps@reduced graphene oxide paper-based electrochemical sensor is high, and the surface of reduced graphene can be well observed to be uniformly modified by nano gold under a scanning electron microscope. From the raman spectrum of fig. 3, it can be seen that the modification of the nano gold product is on the surface of the reduced graphene oxide. As can be seen from fig. 6 (a), the sensor prepared in example 1 has excellent electrochemical activity, and can clearly detect the redox peak signal of potassium ferricyanide.
Example 2
Preparation of Au NPs@reduced graphene oxide paper-based electrochemical sensor:
(1) Preparation of graphene oxide paper:
1.4g of cellulose pulp was dispersed in 1L of water and stirred rapidly at room temperature; adding 60mL of graphene oxide solution with the concentration of 15g/L, and continuously stirring to uniformly mix the graphene oxide and cellulose; adding 2ml of chitosan with the concentration of 1wt% as a binding agent, and continuously stirring until water becomes clear, so that graphene oxide is completely compounded on the surface of cellulose; pouring the mixed slurry into a paper sheet forming machine, and forming and drying to obtain graphene oxide paper;
(2) Adsorbing gold ions:
immersing the graphene oxide paper in the step (1) in 1g/L chloroauric acid solution for 10min, so that the graphene oxide paper fully absorbs the chloroauric acid solution;
(3) Patterning and reducing chloroauric acid and graphene oxide by a laser direct writing method;
taking out the graphene oxide paper adsorbed with the chloroauric acid solution in the step (2), spreading the graphene oxide paper on the surface of glass after no liquid drops drop from the graphene oxide paper, and placing the graphene oxide paper into a laser direct writing machine for pattern reduction, wherein the output power of laser direct writing is 800mW, and the speed is 100mm/s, so that a patterned reduced graphene oxide electrode containing a small amount of gold nanoparticles is obtained;
(4) Growth of nano gold:
and (3) placing the patterned electrode in the step (3) into 1g/L chloroauric acid solution, changing the surface of the electrode from gray to golden yellow after 10min, taking out the electrode, repeatedly flushing the electrode with clear water, and then placing the electrode into an oven for drying to finally obtain the Au NPs@reduced graphene oxide paper-based electrochemical sensor.
(5) Electrochemical detection:
and connecting the working electrode of the prepared Au NPs@reduced graphene oxide paper-based electrochemical sensor with the working electrode of an electrochemical workstation, wherein a counter electrode and a reference electrode are respectively a platinum electrode and a silver/silver chloride electrode. The connected three electrodes were placed in a 1M sodium chloride solution and cycled at a rate of 100mV/s for 30 cycles over a voltage range of-0.2-0.7V. After the voltammograms are matched, 5mM potassium ferricyanide is added and voltammograms are tested using different scan rates over the same voltage range.
Example 3
Preparation of Au NPs@reduced graphene oxide paper-based electrochemical sensor:
(1) Preparation of graphene oxide paper:
1g of cellulose pulp was dispersed in 1L of water and stirred rapidly at room temperature; adding 100mL of graphene oxide solution with the concentration of 5g/L, and continuously stirring to uniformly mix the graphene oxide and cellulose; adding 2ml of dopamine with the concentration of 1wt% as a binding agent, and continuously stirring until water becomes clear, so that graphene oxide is completely compounded on the surface of cellulose; pouring the mixed slurry into a paper sheet forming machine, and forming and drying to obtain graphene oxide paper;
(2) Adsorbing gold ions:
immersing the graphene oxide paper in the step (1) in 2g/L chloroauric acid solution for 1min to enable the graphene oxide paper to fully absorb the chloroauric acid solution;
(3) Patterning and reducing chloroauric acid and graphene oxide by a laser direct writing method;
taking out the graphene oxide paper adsorbed with the chloroauric acid solution in the step (2), spreading the graphene oxide paper on the surface of glass after no liquid drops drop from the graphene oxide paper, and placing the graphene oxide paper into a laser direct writing machine for pattern reduction, wherein the output power of laser direct writing is 200mW, and the speed is 50mm/s, so that a patterned reduced graphene oxide electrode containing a small amount of gold nanoparticles is obtained;
(4) Growth of nano gold:
and (3) placing the patterned electrode in the step (3) into 5g/L chloroauric acid solution, changing the surface of the electrode from gray to golden yellow after 60min, taking out the electrode, repeatedly flushing the electrode with clear water, and then placing the electrode into an oven for drying to finally obtain the Au NPs@reduced graphene oxide paper-based electrochemical sensor.
(5) Electrochemical detection:
and connecting the working electrode of the prepared Au NPs@reduced graphene oxide paper-based electrochemical sensor with the working electrode of an electrochemical workstation, wherein a counter electrode and a reference electrode are respectively a platinum electrode and a silver/silver chloride electrode. The connected three electrodes were placed in a 1M sodium chloride solution and cycled at a rate of 100mV/s for 30 cycles over a voltage range of-0.2-0.7V. After the voltammograms are matched, 5mM potassium ferricyanide is added and voltammograms are tested using different scan rates over the same voltage range.
Example 4
Preparation of Au NPs@reduced graphene oxide paper-based electrochemical sensor:
(1) Preparation of graphene oxide paper:
dispersing 2g of cellulose pulp in 1L of water, and rapidly stirring at room temperature; adding 60mL of graphene oxide solution with the concentration of 15g/L, and continuously stirring to uniformly mix the graphene oxide and cellulose; adding 2ml of polyethyleneimine with the concentration of 1wt% as a binding agent, and continuously stirring until water becomes clear, so that graphene oxide is completely compounded on the surface of cellulose; pouring the mixed slurry into a paper sheet forming machine, and forming and drying to obtain graphene oxide paper;
(2) Adsorbing gold ions:
immersing the graphene oxide paper in the step (1) in 2g/L chloroauric acid solution for 1min to enable the graphene oxide paper to fully absorb the chloroauric acid solution;
(3) Patterning and reducing chloroauric acid and graphene oxide by a laser direct writing method;
taking out the graphene oxide paper adsorbed with the chloroauric acid solution in the step (2), spreading the graphene oxide paper on the surface of glass after no liquid drops drop from the graphene oxide paper, and placing the graphene oxide paper into a laser direct writing machine for pattern reduction, wherein the output power of laser direct writing is 600mW, and the speed is 100mm/s, so that a patterned reduced graphene oxide electrode containing a small amount of gold nanoparticles is obtained;
(4) Growth of nano gold:
and (3) placing the patterned electrode in the step (3) into 5g/L chloroauric acid solution, changing the surface of the electrode from gray to golden yellow after 20min, taking out the electrode, repeatedly flushing the electrode with clear water, and then placing the electrode into an oven for drying to finally obtain the Au NPs@reduced graphene oxide paper-based electrochemical sensor.
(5) Electrochemical detection:
and connecting the working electrode of the prepared Au NPs@reduced graphene oxide paper-based electrochemical sensor with the working electrode of an electrochemical workstation, wherein a counter electrode and a reference electrode are respectively a platinum electrode and a silver/silver chloride electrode. The connected three electrodes were placed in a 1M sodium chloride solution and cycled at a rate of 100mV/s for 30 cycles over a voltage range of-0.2-0.7V. After the voltammograms are matched, 5mM potassium ferricyanide is added and voltammograms are tested using different scan rates over the same voltage range.
Comparative example 1
Preparation of Au NPs@reduced graphene oxide paper-based electrochemical sensor:
(1) Preparation of graphene oxide paper:
1.4g of cellulose pulp was dispersed in 1L of water and stirred rapidly at room temperature; adding 60mL of graphene oxide solution with the concentration of 10g/L, and continuously stirring to uniformly mix graphene oxide and cellulose; adding 2ml of cationic polyacrylamide with the concentration of 1wt% as a binding agent, and continuously stirring until water becomes clear, so that graphene oxide is completely compounded on the surface of cellulose; pouring the mixed slurry into a paper sheet forming machine, and forming and drying to obtain graphene oxide paper;
(2) Adsorbing gold ions:
immersing the graphene oxide paper in the step (1) in ultrapure water for 1min to enable the graphene oxide paper to fully absorb water;
(3) Patterning and reducing chloroauric acid and graphene oxide by a laser direct writing method;
taking out the graphene oxide paper adsorbed with the chloroauric acid solution in the step (2), spreading the graphene oxide paper on the surface of glass after no liquid drops drop from the graphene oxide paper, and placing the graphene oxide paper into a laser direct writing machine for pattern reduction, wherein the output power of laser direct writing is 700mW, and the speed is 20mm/s, so that a patterned reduced graphene oxide electrode containing a small amount of gold nanoparticles is obtained;
(4) Growth of nano gold:
and (3) putting the patterned electrode in the step (3) into 1g/L chloroauric acid solution, taking out the electrode after 30min, repeatedly flushing with clear water, putting into a drying oven, and drying to finally obtain the Au NPs@reduced graphene oxide paper-based electrochemical sensor.
As can be seen from fig. 4, the prepared sensor surface does not show golden yellow, because no chloroauric acid solution is soaked in the step (2) so that no nano gold is inoculated on the reduced graphene oxide surface in the laser direct writing process, thus affecting the growth of the subsequent nano gold.
Comparative example 2
Preparation of Au NPs@reduced graphene oxide paper-based electrochemical sensor:
(1) Preparation of graphene oxide paper:
1.4g of cellulose pulp was dispersed in 1L of water and stirred rapidly at room temperature; adding 60mL of graphene oxide solution with the concentration of 10g/L, and continuously stirring to uniformly mix graphene oxide and cellulose; adding 2ml of cationic polyacrylamide with the concentration of 1wt% as a binding agent, and continuously stirring until water becomes clear, so that graphene oxide is completely compounded on the surface of cellulose; pouring the mixed slurry into a paper sheet forming machine, and forming and drying to obtain graphene oxide paper;
(2) Adsorbing gold ions:
immersing the graphene oxide paper in the step (1) in ultrapure water for 1min to enable the graphene oxide paper to fully absorb water;
(3) Patterning and reducing chloroauric acid and graphene oxide by a laser direct writing method;
taking out the graphene oxide paper adsorbed with the chloroauric acid solution in the step (2), spreading the graphene oxide paper on the surface of glass after no liquid drops drop from the graphene oxide paper, and placing the graphene oxide paper into a laser direct writing machine for pattern reduction, wherein the output power of laser direct writing is 500mW, and the speed is 20mm/s, so as to obtain a patterned reduced graphene oxide electrode containing a small amount of gold nanoparticles;
(4) Growth of nano gold:
and (3) putting the patterned electrode in the step (3) into ultrapure water, taking out the electrode after 30min, repeatedly flushing with clear water, putting into an oven for drying, and finally obtaining the reduced graphene oxide paper-based electrochemical sensor.
(5) Electrochemical detection:
and connecting the working electrode of the prepared Au NPs@reduced graphene oxide paper-based electrochemical sensor with the working electrode of an electrochemical workstation, wherein a counter electrode and a reference electrode are respectively a platinum electrode and a silver/silver chloride electrode. The connected three electrodes were placed in a 1M sodium chloride solution and cycled at a rate of 100mV/s for 30 cycles over a voltage range of-0.2-0.7V. After the voltammograms are matched, 5mM potassium ferricyanide is added and voltammograms are tested using different scan rates over the same voltage range.
As can be seen from fig. 5, the prepared reduced graphene oxide paper-based electrochemical sensor pattern is gray. As is clear from the graph (b) of FIG. 6, the sensor prepared in comparative example 2 has no modification of nano gold, and thus has poor electrode activity, and thus does not detect the redox peak signal of potassium ferricyanide.
The surface sheet resistance test of the graphene oxide prepared in the above three examples and step (1) is shown in table 1.
TABLE 1 results of sheet resistance tests for different examples
Sensing detection of Au NPs@reduced graphene oxide paper-based electrochemical sensor on hydrogen peroxide
(1) Activating electrode
The electrochemical sensor prepared in example 1 was placed in a phosphate buffer solution and subjected to a voltammetric test. The test conditions were cycled for 30 cycles at a rate of 100mV/s over a voltage range of-0.8-0.6V. Until the voltammograms overlap, the electrode activation is complete.
(2) Hydrogen peroxide detection
The time current test method is adopted, the test condition is-0.6V, and the time is 1200s. Hydrogen peroxide is added into the solution at intervals of 50s, so that the concentration of the hydrogen peroxide is increased proportionally.
(3) Tamper-resistant test
The time current test method is adopted, the test condition is-0.6V, and the time is 400s. Hydrogen peroxide, ascorbic acid, uric acid, dopamine, glucose and hydrogen peroxide are respectively added into the solution at intervals, and the change of current is observed.
As shown in FIG. 7, the prepared paper-based electrochemical sensor can be well used for sensing and detecting hydrogen peroxide. (a) For a time current curve of hydrogen peroxide detection, it can be seen that the sensor shows good step current characteristics along with the increase of hydrogen peroxide concentration when detecting hydrogen peroxide, and obvious current change can be generated by adding 20 mu M hydrogen peroxide; (b) For the anti-interference test of hydrogen peroxide detection, it can be seen that the prepared sensor only generates obvious current change when hydrogen peroxide is added, and interference generated by other substances can be well avoided.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the nanogold@reduced graphene oxide paper-based electrochemical sensor is characterized by comprising the following steps of:
(1) Preparation of graphene oxide paper:
dispersing cellulose pulp in water, adding graphene oxide, and continuously stirring to uniformly mix the graphene oxide and cellulose; adding a bonding agent, and continuously stirring until the water becomes clear to obtain slurry; pouring the slurry into a paper sheet forming machine for papermaking, and drying to obtain graphene oxide paper;
(2) Adsorbing gold ions:
immersing the graphene oxide paper in the step (1) in chloroauric acid solution to enable the graphene oxide paper to fully absorb the chloroauric acid solution;
(3) Patterning and reducing chloroauric acid and graphene oxide by a laser direct writing method;
spreading the graphene oxide paper adsorbed with the chloroauric acid solution in the step (2) on the surface of glass, and placing the graphene oxide paper into a laser direct writing machine for patterning reduction to obtain a patterned reduced graphene oxide electrode containing nano gold particles;
(4) Growth of nano gold:
and (3) placing the patterned reduced graphene oxide electrode containing the nano gold particles in the step (3) into chloroauric acid solution, and finally obtaining the Au NPs@reduced graphene oxide paper-based electrochemical sensor after the surface of the electrode is changed from gray to golden yellow and dried.
2. The method for preparing the nanogold@reduced graphene oxide paper-based electrochemical sensor according to claim 1, which is characterized by comprising the following steps of:
the binding agent in the step (1) is at least one of cationic polyacrylamide, chitosan, dopamine and polyethyleneimine;
the concentration of the binding agent in the slurry in the step (1) is 0-1wt% and is not 0.
3. The method for preparing the nanogold@reduced graphene oxide paper-based electrochemical sensor according to claim 1, which is characterized by comprising the following steps of: the concentration of the cellulose pulp in the step (1) is 0.05wt% to 0.3wt%.
4. The method for preparing the nanogold@reduced graphene oxide paper-based electrochemical sensor according to claim 1, which is characterized by comprising the following steps of: the concentration of graphene in the slurry in the step (1) is 0.5g/L-15g/L.
5. The method for preparing the nanogold@reduced graphene oxide paper-based electrochemical sensor according to claim 1, which is characterized by comprising the following steps of: the concentration of the chloroauric acid solution in the step (2) is 0-5g/L and is not 0.
6. The method for preparing the nanogold@reduced graphene oxide paper-based electrochemical sensor according to claim 1, which is characterized by comprising the following steps of:
and (3) the output power of the laser direct writing machine is 100mW-800mW, and the writing speed is 5mm/s-200mm/s.
7. The method for preparing the nanogold@reduced graphene oxide paper-based electrochemical sensor according to claim 1, which is characterized by comprising the following steps of: the concentration of the chloroauric acid solution in the step (4) is 0.1g/L-5g/L.
8. The method for preparing the nanogold@reduced graphene oxide paper-based electrochemical sensor according to claim 1, which is characterized by comprising the following steps of: the soaking time in the step (2) is 1min-60min, and the time for changing the surface of the electrode from gray to golden is 5min-60min.
9. A nanogold@reduced graphene oxide paper-based electrochemical sensor prepared according to the method of any one of claims 1 to 8.
10. Use of the nanogold @ reduced graphene oxide paper-based electrochemical sensor according to claim 9 in electrochemical sensing of hydrogen peroxide.
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